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CHAPTER 1

LITERATURE SURVEY

In the journal ―Self-powered environmental sensor system driven by
nanogenerators‖ Minbaek Lee, a Joonho Bae, a Joohyung Lee,b Churl-Seung Lee, Seunghun
Hongb and Zhong Lin Wang, says By integrating NGs with a Hg2+ sensor, we could build a
selfpowered environmental sensing device. Note that this detection experiment was
conducted only utilizing our sensing circuit powered by NGs without any auxiliary
equipment such as voltage or current signal amplifiers. In addition, the LED can be replaced
by an RF unit so that the signal can be detected wirelessly over a longer distance. In the
future, our system can be a prototype for environmental sensors which are stand-alone, self-
powering and self- indicating.
Piezoelectric nanogenerators—Harvesting ambient mechanical energy at the nanometer
scale‖ Xudong Wang (Department of Materials Science and Engineering, University of
Wisconsin–Madison, WI 53706, USA). This paper reviews the development of NGs from the
fundamental principles to theoretical predictions to practical devices. Compared to
conventional piezoelectric materialbased mechanical energy harvesters, using NWs would
potentially improve the energy conversion efficiency, enhance the sensitivity to low-level
mechanical energy sources, and extend the device lifetime. ZnO NW is the first nanomaterial
that has been applied for NG development. Leading by the research on ZnO NWs, NWs
made from other piezoelectric materials, including BaTiO3, PZT, and PVDF were also
studied to reveal their mechanical energy conversation capability.
Piezoelectric Energy Harvesting Devices: An Alternative Energy Source forWireless
Sensors Action.‖ Nechibvute, Albert Chawanda, and Pearson Luhanga. The process of
harnessing and converting ambient energy sources into usable electrical energy is called
energy harvesting.Energy harvesting raises the possibility of self-powered systems which are
ubiquitous and truly autonomous, and without human intervention for energy replenishment.
Among the ambient energy sources such as solar energy, heat, and wind, mechanical
vibrations are an attractive ambient source mainly because they are widely available and are
ideal for the use of piezoelectric materials, which have the ability to convert mechanical
strain energy into electrical energy. This paper presents a concise review of piezoelectric
microgenerators and nanogenerators as a renewable energy resource to power wireless
sensors.

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CHAPTER 2
INTRODUCTION

Energy can be stored in a capacitor, super capacitor, or battery. Capacitors are used
when the application needs to provide huge energy spikes. Batteries leak less energy and are
therefore used when the device needs to provide a steady flow of energy.
Current interest in low power energy harvesting is for independent sensor networks. In these
applications an energy harvesting scheme puts power stored into a capacitor then
boosted/regulated to a second storage capacitor or battery for the use in the microprocessor.
The power is usually used in a sensor application and the data stored or is transmitted
possibly through a wireless method.
Nanotechnology is one of the most promising innovations capable of effective energy
harvesting. Nanogenerator is a technology that converts mechanical/thermal energy as
produced by small-scale physical change into electricity. . Both the piezoelectric and
triboelectric nanogenerators can convert the mechanical energy into electricity. However, the
pyroelectric nanogenerators can be used to harvest thermal energy from a time-dependent
temperature fluctuation.

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CHAPTER 3

SOURCES FOR ENERGY HARVESTING

The classification of energy harvesting can be organized on the basis of the form of
energy they use to scavenge the power. The various sources for energy harvesting are wind
turbines, photovoltaic cells, thermoelectric generators and mechanical vibration devices such
as piezoelectric devices, electromagnetic devices etc.
2.1 Mechanical Vibrations
When a device is subjected to vibration, an inertial mass can be used to create
movement. This movement can be converted to electrical energy using three mechanisms:
piezoelectric, electrostatic and electromagnetic. The form of energy utilized here is the
mechanical energy.
2.1.1 Piezoelectric Energy Harvesting
The piezoelectric effect was discovered by J and P Curie in 1880. They found that if
certain crystals were subjected to mechanical strain, they became electrically polarized and
the degree of polarization was proportional to the applied strain. Conversely, these materials
deform when exposed to an electric field. These materials can convert mechanical energy
from pressure, vibrations or force into electricity. This property of piezoelectric materials is
considered by the researchers to develop various piezoelectric harvesters in order to power
different applications. Due to their inherent ability to detect vibrations, piezoelectric materials
have become a viable energy scavenging source. Widely used materials are materials such as
quartz(naturally occurring), Polycrystalline ceramic , Lead Zirconium Titanate . With their
anisotropic characteristics, the properties of the piezoelectric material differ depending upon
the direction of forces and orientation of the polarization and electrodes. The properties of
piezoelectric materials vary with age, stress and temperature. The possible advantages of
using piezoelectric materials are the direct generation of desired voltage since they do not
need a separate voltage source and additional components. These generators are compatible
with the MEMs. These generators are the simplest and can be used in force and impact-
coupled harvesting applications. Some disadvantages are that piezoelectric materials are
brittle in nature and sometimes allow the leakage of charge.

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Fig 2.1 piezoelectric energy harvesting system

Fig 2.2 Two types of piezoelectric energy harvesters (a) d31 mode (b) d33 mode

Piezoelectric energy harvesters can work in either d33 mode or d31 mode as shown in Fig.
2.2. In d31 mode, a lateral force is applied in the direction perpendicular to the polarization
direction. Here the electrodes are on its top and bottom surfaces of the bending beam as in
Fig. 2.2(a). In d33 mode, force applied is in the same direction as the polarization direction
but has all electrodes on its top surfaces as in Fig. 2.2(b). Although piezoelectric materials in
d31 mode normally have a lower coupling coefficients than in d33 mode, d31 mode is more
commonly used. This is because when a cantilever or a double-clamped beam (two typical
structures in vibration energy harvesters) bends, more lateral stress is produced than
vertical stress, which makes it easier to couple in d31 mode.

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CHAPTER 3

NANOGENERATOR

Nanogenerator technology is one of the most promising ways to harvest energy by
converting mechanical/thermal energy as produced by small-scale physical change into
electricity. Nanogenerator has three typical approaches: piezoelectric, triboelectric, and
pyroelectric nanogenerators. Both the piezoelectric and triboelectric nanogenerators can
convert the mechanical energy into electricity. However, the pyroelectric nanogenertors can
be used to havest thermal energy from a time-dependent temperature fluctuation.

Nanowires
Piezoelectric nanowires (NWs) are the building blocks of NGs. NW is a one
dimensional (1D) nanomaterial that typically has a diameter less than 100 nm and a length
more than 1 mm. Most ceramic NWs are single crystals. Compared to the conventional thin-
film-based piezoelectric cantilever transducers, using piezoelectric NWs for mechanical
energy scavenging offers three unique advantages:
(1) Enhanced piezoelectric effect. 400–500% enhancement of the piezoelectric effect was
predicted due to the flexoelectric effect [18], when a strain gradient is experienced by a
ferroelectric NW with a thickness of a few tens of nanometres’.
(2) Superior mechanical properties. The lattice perfection of NWs enables much larger
critical strain, higher flexibility, and longer operational lifetime.
(3) High sensitivity to small forces. Large aspect ratio and small thickness allow the creation
of significant strain in the NWs under a force at the nano-Newton or even pico-Newton level.
3.1 piezoelectric nanogenerator
Piezoelectric Nanogenerator is an energy harvesting device converting the external
kinetic energy into an electrical energy based on the energy conversion by nano-structured
piezoelectric material. Although its definition may include any types of energy harvesting
devices with nano-structure converting the various types of the ambient energy (e.g. solar
power and thermal energy), it is used in most of times to specifically indicate the kinetic
energy harvesting devices utilizing nano-scaled piezoelectric material.
Although still in the early stage of the development, it has been regarded as a potential
breakthrough toward the further miniaturization of the conventional energy harvester,
possibly leading the facile integration with the other types of energy harvester converting the
different types of energy and the independent operation of mobile electronic devices with the
reduced concerns for the energy source, consequently.

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CHAPTER 4

MECHANISM OF PIEZOELECTRIC NANOGENERATORS

Fig 3.1 Working principle of nanogenerator where an individual nanowire is subjected to the
force exerted perpendicular to the growing direction of nanowire. (a) An AFT tip is swept
through the tip of the nanowire. Only negatively charged portion will allow the current to
flow through the interface. (b) The nanowire is integrated with the counter electrode with
AFT tip-like grating. As of (a), the electrons are transported from the compressed portion of
nanowire to the counter electrode because of Schottky contact.

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Fig 3.2 Working principle of nanogenerator where an individual nanowire is subjected to the
force exerted parallel to the growing direction of nanowire.

The working principle of nanogenerator will be explained for 2 different cases: the force exerted
perpendicular and parallel to the axis of the nanowire.

The working principle for the first case is explained by a vertically grown nanowire subjected
to the laterally moving tip (fig 3.1). When a piezoelectric structure is subjected to the external
force by the moving tip, the deformation occurs throughout the structure. The piezoelectric
effect will create the electrical field inside the nanostructure; the stretched part with the
positive strain will exhibit the positive electrical potential, whereas the compressed part with
the negative strain will show the negative electrical potential. This is due to the relative
displacement of cations with respect to anions in its crystalline structure. As a result, the tip
of the nanowire will have an electrical potential distribution on its surface, while the bottom
of the nanowire is neutralized since it is grounded. The maximum voltage generated in the
nanowire can be calculated by the following equation:

where κ0 is the permittivity in vacuum, κ is the dielectric constant, e33, e15 and e31 are the
piezoelectric coefficients, ν is the Poisson ratio, a is the radius of the nanowire, l is the length
of the nanowire and νmax is the maximum deflection of the nanowire's tip.

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The electrical contact plays an important role to pump out charges in the surface of the tip.
The schottky contact must be formed between the counter electrode and the tip of the
nanowire since the ohmic contact will neutralize the electrical field generated at the tip. In
order to form an effective schottky contact, the electron affinity(Ea) must be smaller than the
work function(φ) of the metal composing the counter electrode. For the case of ZnO
nanowire with the electron affinity of 4.5 eV, Pt (φ=6.1eV) is a suitable metal to construct the
schottky contact. By constructing the schottky contact, the electrons will pass to the counter
electrode from the surface of the tip when the counter electrode is in contact with the regions
of the negative potential, whereas no current will be generated when it is in contact with the
regions of the positive potential, in the case of n-type semiconductive nanostructure (p-type
semiconductive structure will exhibit the reversed phenomenon since the hole is mobile in
this case). The formation of the schottky contact also contributes to the generation of direct
current output signal consequently.
For the second case (Fig 3.2), a model with a vertically grown nanowire stacked between the
ohmic contact at its bottom and the schottky contact at its top is considered. When the force is
applied toward the tip of the nanowire, the uniaxial compressive is generated in the nanowire.
Due to the piezoelectric effect, the tip of the nanowire will have a negative piezoelectric
potential, increasing the Fermi level at the tip. Since the electrons will then flow from the tip

to the bottom through the external circuit as a result, the positive electrical potential will be
generated at the tip. The schottky contact will barricade the electrons being transported
through the interface, therefore maintaining the potential at the tip. As the force is removed,
the piezoelectric effect diminishes, and the electrons will be flowing back to the top in order
to neutralize the positive potential at the tip. The second case will generate alternating current
output signal

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CHAPTER 5

GEOMETRICAL CONFIGURATION

Depending on the configuration of piezoelectric nanostructure, the most of the nanogenerator can
be categorized into 3 types: VING, LING and "NEG".

(a) Vertical nanowire Integrated Nanogenerator (VING).

Fig 3.3 Schematic view of typical Vertical nanowire Integrated Nanogenerator, (a) with full
contact, and (b) with partial contact. Note that the grating on the counter electrode is
important in the latter case.
VING is a 3-dimensional configuration consisting of a stack of 3 layers in general, which are
the base electrode, the vertically grown piezoelectric nanostructure and the counter electrode.
The piezoelectric nanostructure is usually grown from the base electrode by various
synthesizing techniques, which are then integrated with the counter electrode in full or partial
mechanical contact with its tip.
The first VING utilizes the counter electrode with the periodic surface grating resembling the
arrays of AFM tip as a moving electrode. Since the counter electrode is not in full contact
with the tips of the piezoelectric nanowire, its motion in-plane or out-of-plane occurred by
the external vibration induces the deformation of the piezoelectric nanostructure, leading to
the generation of the electrical potential distribution inside each individual nanowire. It
should be noted that the counter electrode is coated with the metal forming the schottky
contact with the tip of the nanowire, where only the compressed portion of piezoelectric
nanowire would allow the accumulated electrons pass through the barrier between its tip and
the counter electrode, in case of n-type nanowire. The switch-on and –off characteristic of
this configuration shows its capability of generating direct current generation without any
requirement for the external rectifier.

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In VING with partial contact, the geometry of the counter electrode plays an important role.
The flat counter electrode would not induce the sufficient deformation of the piezoelectric
nanostructures, especially when the counter electrode moves by in-plane mode. After the
basic geometry resembling the array of AFM tips, a few other approaches have been followed
for facile development of the counter electrode. Counter electrode composed of ZnO
nanorods utilizing the similar technique used for synthesizing ZnO nanowire array are
generated.
(b) Lateral nanowire Integrated Nanogenerator (LING).

Fig 3.4 Schematic view of typical Lateral nanowire Integrated Nanogenerator
LING is a 2-dimensional configuration consisting of three parts: the base electrode, the
laterally grown piezoelectric nanostructure and the metal electrode for Schottky contact. In
most of cases, the thickness of the substrate film is much thicker than the diameter of the
piezoelectric nanostructure, so the individual nanostructure is subjected to the pure tensile
strain.
LING is an expansion of single wire generator (SWG), where a laterally aligned nanowire is
integrated on the flexible substrate. SWG is rather a scientific configuration used for
verifying the capability of electrical energy generation of a piezoelectric material and is
widely adopted in the early stage of the development.
As of VINGs with full mechanical contact, LING generates AC electrical signal. The output
voltage can be amplified by constructing an array of LING connected in series on the single
substrate, leading the constructive addition of the output voltage. Such a configuration may
lead to the practical application of LING for scavenging large-scale power, for example, wind
or ocean waves.

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(c) Nanocomposite Electrical Generators (NEG).

Fig 3.5 Schematic view of typical Nanocomposite Electrical Generator “NEG" is a 3-
dimensional configuration consisting three main parts: the metal plate electrodes, the
vertically grown piezoelectric nanostructure and the polymer matrix which fills in between in
the piezoelectric nanostructure.
NEG was introduced by Momeni et al.[7] It was shown that NEG has a higher efficiency compared to
original nanogenerator configuration which a ZnO nanowire will be bended by an AFM tip. It is also
shown that it provides an energy source with higher sustainability.

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CHAPTER 6
MATERIALS USED IN PIEZOELECTRIC NANOGENERATORS

Among various piezoelectric materials studied for the nanogenerator, many of the
researches have been focused on the materials with wurtzite structure such as ZnO, CdS[9]
and GaN.[10]
The greatest advantage of theses material arises from the facile and cost-effective fabrication
technique, hydrothermal synthesis. Since the hydrothermal synthesis can be conducted in a
low temperature environment under 100°C in addition to vertical and crystalline growth,
these materials can be integrated in various substrates with reduced concern for its physical
characteristics such as a melting temperature.
Endeavors for enhancing the piezoelectricity of the individual nanowire also led to the
development of other piezoelectric materials based on Wurtzite structure. In recently
introduced p-type ZnO nanowire, unlike the n-type semiconductive nanostructure, the mobile
particle in p-type is a hole, thus the schottky behavior is reversed from that of n-type case; the
electrical signal is generated from the portion of the nanostructure where the holes are
accumulated. It is experimentally proved that p-type ZnO nanowire can generate the output
signal near 10 times that of n-type ZnO nanowire.
From the idea that the material with perovskite structure is known to have more effective
piezoelectric characteristic compared to that with wurtzite structure, Barium titanate
(BaTiO3) nanowire has been developed whose output signal is found to be more than 16 time
that from a similar ZnO nanowire.
Recent studies in this field suggested that PVDF can be also applied to form a nanogenerator.
Being a polymer, PVDF utilizes a near-field electrospinning for its fabrication, which is
rather a different technique compared to other materials. The nanofiber can be directly
written on the substrate controlling the process, and this technique is expected to be applied
for forming self-powered textile based on nanofiber.

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CHAPTER 6

APPLICATIONS OF PIEZOELECTRIC GENERATORS

Nanogenerator is expected to be applied for various applications where the periodic kinetic
energy exists, such as wind and ocean waves in a large scale to the muscle movement by the
beat of a heart or inhalation of lung in a small scale. The further feasible applications are as
follows.
(a) Self-powered nano/micro devices: One of the feasible applications of nanogenerator is
an independent or a supplementary energy source to nano/micro devices consuming relatively
low amount of energy in a condition where the kinetic energy is supplied continuously. One
of example has been introduced by Professor Zhong Lin Wang‘s group in 2010 by the self-
powered pH or UV sensor integrated VING with an output voltage of 20~40 mV onto the
sensor.
Still, the converted electrical energy is relatively small for operating nano/micro devices;
therefore the range of its application is still bounded as a supplementary energy source to the
battery. The breakthrough is being sought by combining the nanogenerator with the other
types of energy harvesting devices, such as solar cell or biochemical energy
harvester.[14][15]
This approach is expected to contribute to the development of the energy source suitable for
the application where the independent operation is crucial, such as Smart dust.
(b) Smart Wearable Systems: The outfit integrated or made of the textiles with the
piezoelectric fibre is one of the feasible applications of the nanogenerator. The kinetic energy
from the human body is converted to the electrical energy through the piezoelectric fibres,
and it can be possibly applied to supply the portable electronic devices such as health-
monitoring system attached with the Smart Wearable Systems. The nanogenerator such as
VING can be also easily integrated in the shoe employing the walking motion of human
body.
Another similar application is a power-generating artificial skin. Professor Zhong Lin Wang‘s
group has shown the possibility by generating AC voltage of up to 100 mV from the flexible
SWG attached to the running hamster.
(c) Transparent and Flexible Devices. Some of the piezoelectric nanostructure can be
formed in various kinds of substrates, such as flexible and transparent organic substrate. The
research groups in SKKU (Professor Sang-Woo Kim‘s group) and SAIT (Dr. Jae-Young
Choi‘s group) have developed the transparent and flexible nanogenerator which can be
possibly used for self-powered tactile sensor and anticipated that the development may be
extended to the energy-efficient touch screen devices. Their research focus is being extended
to enhance the transparency of the device and the cost-effectiveness by substituting Indium-
Tin-Oxide (ITO) electrode with a graphene layer.

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(d) Implantable Telemetric Energy Receiver. The nanogenerator based on ZnO nanowire
can be applied for implantable devices since ZnO not only is bio-compatible but also can be
synthesized upon the organic substrate, rendering the nanogenerator bio-compatible in
overall. The implantable device integrated with the nanogenerator can be operated by
receiving the external ultrasonic vibration outside the human body, which is converted to the
electrical energy by the piezoelectric nanostructure.

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CHAPTER 7
CASE STUDY ON A SELF-POWERED ENVIRONMENTAL SYSTEM DRIVEN BY
NANOGENERATORS

A self powered piezoelectric nanogenerator developed to power up an environment sensor
which detects the presence of toxic Hg2+ ions is described in this case study. The ZnO
nanowires forms the basic unit of the generator used. Other than the nanogenerator, the
system consists of a rectification circuit, a capacitor for charge storage, a signal transmission
LED light and a carbon nanotube-based Hg2+ ion sensor. The circuit lights up the LED
indicator and varying intensities of illumination represents different Hg2+ ion concentration
in the water solution. It is the first demonstration of a nanomaterial-based, self-powered
sensor system for detecting a toxic pollutant.
Being eco friendly and biologically compatible ZnO nanowires (NWs) are best suited for the
fabrication of nanogenerator used here. The flexible Kaplan used as the substrate material
plays a crucial role in improving the performance of the NG since it enhances the effective
contacts between the ends of the piezoelectric ZnO NWs and the Au electrodes. Once the
NWs are uniaxially compressed, a piezoelectric potential drop is created along their lengths,
which drives the flow of electrons in the external load. A dynamic and cycled compressing
and releasing of strain over the NWs results in a synchronized back and forth flow of
electrons. The alternating current thus produced is rectified and stored in a super-capacitor.
The sensor used was composed of single-walled carbon nanotube (SWNT) networks and
SWNT field effect transistors (FETs) with enhancement-mode were used to effectively use
the stored electricity. When mercury ions in water approached the SWNT FET, it turns on the
FET which enables current flow in the circuit. Finally, the attached LED will be lit up with
the different intensities depending on the concentration of toxic materials. The LED indicator
may be replaced by an RF unit in the future so that the signal can be detected wirelessly over
a longer distance. Furthermore, it may inspire the development of a future self-powered
sensor for unreachable or access-denied extreme environments.

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CHAPTER 8

CONSTRUCTION OF PIEZOELECTRIC NANO GENERATOR

NANOGENERATOR
Two simple principles were employed during the construction of the high performance NGs. First is
to stack the multiple NGs along the central axis of nanowires and the next is to use a flexible substrate
to enhance the number of effective NWs in the generator. Crystallographic structure of NWs
in NGs is another very important factor to be considered because it determines the displacement of
ionic distribution in the crystal which eventually results in averaged piezoelectric potential on the
macroscopic scale. Now NWs with wurtzite crystal structure are known to grow uniaxially parallel to
the central axis. This growth property of the NWs helps to integrate multiple NGs based on ZnO NWs
along the central axis or parallel to the central axis. Usually methods such as e-beam lithography,
photolithography or laser patterning are used to grow a fully aligned/uniform ZnO NW array since
non uniformity results in few active contacts between metal electrode and NWs on the solid substrate.
This limitation can be resolved by replacing solid substrates with flexible ones, thus those can follow
the morphology of a relatively non-uniform NW array.
The density of ‗effective NWs‘ in NGs is also a significant parameter to affect their output power. In
a NG, we can define ‗effective NWs‘ as fully contacting NWs in between two electrodes. When an
external stress is applied, only contacted NWs can be effectively under compression/pressure, so that
they contribute a potential difference between the two electrodes. To increase the number of
contacting NWs in the generator, flexible Kapton layers are employed as substrates for both the ZnO
NW array and Au electrode. Flexible substrates can follow the height profiles of the NW forest and
make effective contacts between the ends of NWs and electrodes. Since flexible Kapton layers (50.8
µm) served as substrates for all parts in our fabrication, it can be freely bent or deformed and is well
Exemplified in fig 8.1.

Fig
Fig 8.1 Schematic diagram and scanning electron microscopy (SEM) images of the fabricated
nanogenerator.

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(a) Schematic diagram depicting the structure of a fabricated nanogenerator on flexible
substrates. Both the ZnO NW array and Au film were made on Kapton substrates with high
flexibility.
(b) Low magnification SEM image of a junction between the ZnO NW array and Au film of a
fabricated nanogenerator.
(c) Intermediate magnification SEM image of a junction between the ZnO NW array and Au
film of a fabricated nanogenerator.
(d) High magnification SEM image of a ZnO NW array. The ZnO NW forest shows only
moderate alignment.

8.2 SUPER CAPACITORS
Only by integrating the nanogenerator with a energy storage device will form a power
cell for periodically actuated sensing devices that usually have a relatively long standby mode
and a short active mode. To fulfil this purpose a super capacitor based on multi-walled CNT
(MWNT) coated ITO electrodes and PVA/H3PO4 electrolyte is fabricated. Direct spray
coating method was applied to make uniformly dispersed MWNT layers on ITO glass
substrates (Fig 4.2). The working and counter electrodes were MWNT coated ITO glass
substrates. The electrolyte used was PVA/H3PO4 polymer like solution. The right upper inset
in Fig 4.2a shows a schematic diagram depicting the structure of a super-capacitor fabricated
here.

Fig. 8.2a schematic diagram depicting the structure of a super-capacitor

To store the generated charge from NGs, a super-capacitor and 10-layer-integrated NGs were
connected with a rectifying bridge (inset in Fig 4.2b). The generated AC outputs from NGs
were rectified into direct-current (DC) signals, which directly resulted in the charging process
in a super-capacitor.After charging for ~1 h by applying mechanical vibration to NGs with a

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frequency of 10 Hz and a displacement of ~1.2 cm, a discharge measurement was conducted
to evaluate the stored energy. It was found that the accumulated amount of charge was~3.6×
10-4 C, ensuring that it could be applied to an environmental sensing system. It implies that,
output appropriate enough to power an environmental sensor which detects pollutants
periodically can be generated and stored using the nanogenerator and super capacitor
fabricated respectively.

Fig 8.2b potential-time graph(inset: circuit composed of super capacitor, NG & rectifying bridge

8.3 SENSOR
A self powered environmental sensor was fabricated which can detect Hg2+ ions and indicate
its concentration via the intensity of an LED. Single Walled Carbon Nanotubes (SWCNT)
based FET was used for this purpose. A SWNT network based sensor array was fabricated in
a 4 inch wafer by using the chemical patterning method. Fig 2.3a shows a photograph image
of a fabricated sensor array on a 4 inch SiO2 wafer.

Fig 8.3a: image of a fabricated sensor array on a 4 inch SiO2 wafer.

SWNT network based FETs can be in either enhancement mode or depletion mode since the
network is composed of metallic and semiconducting SWNTs. In our sensor fabrication, the
density of SWNT networks was intended to be relatively low (Fig.2.3b) because networks
with low density tend to be in enhancement mode.

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Fig 8.3b

By integrating NGs with a Hg2+ sensor, we could build a self powered environmental
sensing device. Fig.2.3d shows a circuit diagram. A light emitting diode was attached on the
circuit to serve as an indicator for Hg2+ detection. To accomplish self-powered sensing of
environmental pollutants with NGs, a circuit was designed with two independent loops. In the
energy harvesting process, a circuit was connected in loop A‘(Fig. 4d) with NGs and
rectifying diode bridge to store generated charge in the capacitor (1000 mF, Nichicon). After
a sufficient charging process, the connection was changed to loop ‗B‘ in Fig.2.3d, thus it was
ready to detect Hg2+ ions and light up an LED with a certain intensity depending on the
concentration of pollutants in the water droplet.

Fig 8.2c: circuit diagram

The working principle of our sensor is the difference in standard potential between

SWNTs(E0SWNT= 0.5–0.8 V versus NHE) and Hg2+ ions (E0 Hg2+= 0.8535 V versus NHE).

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8.4 EXPERIMENT
Fig. 4.3 shows photograph images of an LED that was lit up under each concentration of
Hg2+ ions in the water droplets. In this experiment, six capacitors were charged individually
for ~1 h using 10-layer integrated NGs (10 Hz, 1.2 cm peak-to-peak vibration distance).
Charged capacitors were connected in series to supply sufficient voltage (~3 V) for operation
of a SWNT FET-based sensor and an LED all together. There was no external electric power
source in our system. Hg2+ ions were injected in water droplets in sequential steps from 1
nM to 1 mM. All detection procedures were conducted for ~30 s to observe intensity changes
of the LED under constant power from capacitors. To minimize any power dissipation during
sequential detection procedures, observation started from low concentration to high
concentration. At lower concentrations of Hg2+ ions in water droplets, less power (V2/R)
was expected to be used for the sensing operation due to the relatively high resistance in the
circuit (see also Fig. 4.2e (inset) and 4.4i). As shown after the third image of Fig. 4.3,
noticeable LED light appeared from the concentration of 10 nM and got brighter gradually
until those of1 mM. Note that this detection experiment was conducted only utilizing the
sensing circuit powered by NGs without any auxiliary equipment such as voltage or current
signal amplifiers. In addition, the LED can be replaced by an RF unit so that the signal can be
detected wirelessly over a longer distance. In the future, our system can be a prototype for
environmental sensors which are stand-alone, self-powering and self- indicating.

Fig 8.4 a: images of an LED lit up under each concentration of Hg2+ ions in the water
droplets.

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8.5 RESULTS AND DISSCUSSION

Fig 8.5a: Electrical characteristics of fabricated nanogenerators as they are periodically
strained and released. (a) Open-circuit voltage output of a fabricated nanogenerator. (b)
Closed-circuit current output of a fabricated nanogenerator. (c) Open-circuit voltage output of
ten-layer integrated nanogenerators. (d) Closed-circuit current output of ten-layer integrated
nanogenerators. (e) Rectified open-circuit voltage output of ten-layer integrated
nanogenerators. (f) Rectified closed-circuit current output of ten-layer integrated
nanogenerators.
Fig 8.5c and b above shows the open-circuit voltage and closed-circuit current, respectively.
A single NG with a surface area of ~0.8 cm2 reached an output voltage of ~350 mV and a
current of ~125 nA cm-2. These values are much higher than usual values obtained. The
enhanced voltage and current outputs from the NGs can be attributed to the fact that the NGs
on the flexible substrate are able to make a much improved number of contacts between NWs
and electrode.
Fig. 8.5 c and d show output signals from a 10-layer integrated NG device. The open-circuit
voltage and closed-circuit current reach up to ~2.1 V and ~105 nA (a peak output power
density of ~0.3 mWcm-3), respectively. They are enough to use a rectifying circuit to store
the NG output in any storage system. After integration of NGs and rectifying parts, we could
observe almost the same amount of current output and a slightly reduced voltage output from
NGs. Dissipation of voltage was caused by a rectifying circuit containing four diodes. The
high performance of our NGs was due to the flexibility of substrates which enhanced the

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number of contacts between piezoelectric sources and metal electrodes.The electrochemical
properties of the capacitors in the PVA/H3PO4 electrolyte solution were investigated using a
potentiostat/galvanostat. Fig.4.4g exhibits cyclic voltammetry that shows our device has a
good electrochemical stability and capacitance. The scan range was between 0 and 250 mV
with scan rates of 100 mVs-1. The galvanostatic charge–discharge measurement was also
conducted to characterize the electrochemical performance of the MWNT-based super-
capacitor (Fig.8.4h).

Fig 8.4: g) Cyclic voltammetry of a fabricated super-capacitor, (h) Galvanostatic charge–
discharge graph of the super-capacitor. The drain–source current of a sensor was monitored
in various concentrations of Hg2+ ions in water-droplets to characterize the sensing process.
Fig. 4.4i and the inset show the measured drain–source current and resistance of a sensor in
different concentrations of Hg2+ ions in water droplets. Initially, a small current (<10-8 A)
was only observed as we chosea SWNT FET in enhancement mode. When the concentration
of solution reached about ~10 nM, which is the allowable limit of Hg2+ ions in drinking
water set by most government environmental protection agencies, a noticeable change in the
resistance was observed (see the inset in Fig. 4.c). Sequential injections of Hg2+ led to
discreet changes of the resistance of the sensor.

Fig 8.5i: Sensing behaviour of the fabricated sensor with various concentrations of Hg2+ ions
in water solution. The inset shows the plot of resistance depending on mercury ion injection.

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CHAPTER 9

CONCLUSION

Energy harvesting, captured, and stored for small, wireless autonomous devices, like those
used in wearable electronics and wireless sensor networks is a way to the future what with the
increasing need to devise such measures as would eliminate the crisis encountered in the
energy field. Vibrational Energy Harvesting is the scavenging of energy from low amplitude
low frequency ambient vibrations. Energy is accumulated from ambient vibrations which
could enable smart sensors to be functional indefinitely. Typical power densities available
from energy harvesting devices are highly dependent upon the specific application (affecting
the generator's size) and the design itself of the harvesting generator. In general, for motion
powered devices, typical values are a few µW/cm³ for human body powered applications and
hundreds of µW/cm³ for generators powered from machinery. Most energy scavenging
devices for wearable electronics generate very little power. Nanogenerator is a technology
that converts mechanical/thermal energy as produced by small-scale physical change into
electricity. Both the piezoelectric and triboelectric nanogenerators can convert the mechanical
energy into electricity. However, the pyroelectric nanogenerators can be used to harvest
thermal energy from a time-dependent temperature fluctuation. Vertical nanowire Integrated
Nanogenerator (VING),Lateral nanowire Integrated Nanogenerator (LING), Piezoelectric
Nanogenerator , Nanocomposite Electrical Generators (NEG) have been elaborated. Case
study on a self-powered environmental system driven by nanogenerators has been presented
in detail with pertinent results and discussion to the effect of bringing evidential clarity to the
experiment undertaken. A self powered piezoelectric nanogenerator developed to power up
an environment sensor which detects the presence of toxic Hg2+ ions is described in this case
study. The zno nanowires forms the basic unit of the generator used. Other than the
nanogenerator, the system consists of a rectification circuit, a capacitor for charge storage,
a signal transmission LED light and a carbon nanotube-based Hg2+ ion sensor. The circuit
lights up the LED indicator and varying intensities of illumination represents different Hg2+
ion concentration in the water solution. It is the first demonstration of a nanomaterial-
based, self-powered sensor system for detecting a toxic pollutant.

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CHAPTER 10
REFERENCES

1. Action Nechibvute, Albert Chawanda, Pearson Luhanga; Department of Physics,
Midlands State University, Gweru, Zimbabwe & Department of Physics, University of
Botswana, Gaborone, Botswana ―Piezoelectric Energy Harvesting Devices: An Alternate
Energy Source for Wireless Sensors‖.
2. Minbaek Lee, Joonho Bae, Joohyung Lee, Churl-Seung Lee, Seunghun Hongb and
Zhong Lin Wang ―Self-powered environmental sensor system driven by
nanogenerators‖.(pages 3359-3363)
3. Sravanthi Chalasini & James M Conrad, Electrical and Computer Engineering, University
of North Carolina at Charlotte ―A Survey of Energy Harvesting Sources for Embedded
Systems‖.
4. Xudong Wang, Department of Materials Science and Engineering, University of
Wisconsin–Madison, WI 53706, USA ―Piezoelectric nanogenerators—Harvesting ambient
mechanical energy at the nanometer scale‖.

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